Of basel



pounds of the first phase, but also the unamines, such as aniline, toluidine, naphthyl-I Patented Apr. 19,

-- NITED STATES HERMANN EEITzscHEEnuAEn KEUMM NACHEE, HANS GUBEEE, ANDOTTQKAISER 1,625,531 PATENT OFFICE,

OF BASEL, SWITZERLAND, ASSIGNORS TO SOCIETY OF CHEMICAL INDUSTRY IN EAsLE, 0 BASEL, SWITZERLAND.-

' INTERMEDIATE mam Eon THE SYNTHESIS 0E AZO DYES nun PROCESS 0E MAKING SAME.

compound of the aromatic series having,

firstly, a non-tertiary'amino group, secondly, containing one of a group-of auxochromes including on -CH co N I 3 R CO (wherein LR, and R, represent the same or different alkyl, aryl or aralkyl radicals or a hydrogen atom) and, thirdly, containing still at least one strong acid group, then condensing, in a second phase, at least one molecular proportion of one of a group of compounds which contains an amino or a hydroxy group.

. Ascompounds which may be employed in the first'phase there come-particularly intov consideration the' carboxy-lic. and sulfonic acids of the amino-naphthols,* furthermore the sulfonic and carboxylic acids of the diamines'of the benzene and naphthalene series, their monoacidyl, monoalkyl,monoaralkyl and monoaryl derivatives and their asymmetric dialkyl or diaralkyl derivatives, respectively, the derivatives of the 1-aryl-5- pyrazolone sulfonic and carboxylic acids which carry amino groups in the '-'aryl nucleus. r I

As'compou'nds used in the second phase there may beemployed not only the comsulfonated and uncarboxylated derivatives of same, furthermore primary and secondary amine, the sul fonic and carboxylic acidsof .same,--. diamines, such as" phenylenediamines and toluylenediamines,-nitroanilines, phe-- nols, aininophenol's, nitrophenols furthercourse of the reaction may be followed by more aliphatic amines," as forinstance (liethylamines or aliphatic alcohols, and. finally mm0nia,and.water.- Y These condensations may in most cases be carried out by successively-stirring the components together in' a suitable diluent, and

it was surprising to find that as such a medium water 1s very appropriate. The

f 'No Drawing. Application flied July 20, 1923, Serial No. 652,857, and in Switzerland September 7, 1922.

thequantity of hydrogen halide obtained,"

or by the formation of a precipitate or a vclear solut1on, or by the disappearance of the components.

'There'are thus obtained compounds of the general formula:

Halogen wherein R stands for an aromatic complex which contains one of a group of auxo-f chromes including (R and R, representing the same ordifierent alkyl, aryl or aral l radicals or a hydrogen atom), a: for a ydrogen atom. or an alkyl, aralkyl or aryl residue, one of the two residues m and R containing at least one strong acid group, Q, for ahydrogen atom or to the carbon atom of the cyanuric nucleus by one of a" group of connecting links which contains a radical which are linke O or N, and 'n, for a whole number not higher These new products are colorless solvents forming colorless to yellow andbrownish solutions. They are characterized by the presence of still one mobile atom of halogen at the cyanurionucleus.

present invention,- ing the same.

' Emma 18.5 parts of 'cyanuric chloride .ina fine state of sub-division, a solution of 23"parts of l amino-4-acetylamino3-benzene sulfonic: acid in 200 parts of water, and 13.3 parts of caustic soda solution of 30 per cent strength. are added to 300 parts of water. After a short time a clear solution is formed which: contains the primary condensation product The following examples illustrate-the without, however, limitv from 1 molecular proportion of cyanuric in water. without coloration.

chloride and one molecular proportion of l-aminoe acetylamino 3 benzene sulfonic acid. This solution is exactly neutralized in the cold with dilute caustic soda solution, treated once more with 13.3 parts of caustic soda solution of 30 per cent strength, and stirred until the liquid is again neutral.

The secondary condensation product from one molecular proportion of cyanuric chloride, one, molecular proportion of l-am-inolacetylamino-3-benzene sulfonic acid, and one molecular proportion of water is thus formed.

This product may be precipitated in the form of a light colored precipitate by means of common salt and. acid. It contains still one atom of chlorine and one acetylamino group.

By treatment of the primary condensation product in the cold with ammonia, the secondary condensation product from one molecular proportion "of cyanuric chloride, one molecular proportion of l-amino-i-acetylamino-3-benzene sulfonic acid, and one molecular proportion of ammonia is formed. This product is also a ,grey powder, soluble It contains still one mobile atom of chlorine and one acetylamino group. The replacement of am monia by aniline leads to a product with analogous properties but a little less soluble.

Instead of ammonia or aniline one may also substitute more complicated components. If for instance a solution formed by 15.3- parts of p-aminosalicylic acid, 13.3 parts of caustic soda solution of 30 per cent strength, 30 parts of crystallized sodium.

acetate, and 150 parts of water is added to the crude solution of the rimary condensation product, the secon ary condensation product from 1 molecular proportion of cyanuric chloride, one molecular proportion of p-aminosalicylic acid, and one molecular proportion of 1-amino-4-actylamino-3-benzene sulfonic acid is formed, which is characterized by the presence of one mobile chlorine atom, one acetylamino group, and one external salicylic acid group. It corresponds very probably with the formula v H 011.com i io \\N v coon Q 0.11 an on Example $3.

As the three atoms of halogen of the cyanuric halides react with different rapidity, the cyanuric halide may be added simply to a solution or a mixture of the components of the two phases'of the herein described process, whereby the two stages of the reaction can be exactly followed.

'If for instance 30.2 parts of 1-amino-4- acetylaminonaphthalene-6-sulfonate of sodium in 500 parts of water are stirred with .93 parts of cyanuric chloride in a fine state of subdivision, the mixture being always kept neutralby adding'carefully some sodium carbonate, the primary condensation product is formed first, which precipitates and dissolves again while condensing with a second molecularproportion of acetylnaphthylenediamine sulionic, acid. I

Thesecondary condensation product thus obtained from 1- molecular proportion of cyanuric chloride and two molecular proportions of l-amino-4-acetylaminonaphthalene- 6-sulfonic acid forms a grey powder. which is characterized by the presence of Q-acetylamino groups and 1 mobile atom of chlorine.

By operating in a similar manner there may be obtained secondary condensation products from one'molecular proportion of cyanuric chloride and two molecular proportions of p-phenylenediamine-3-sulfonic acid (gre powder easily soluble in. alkalies),'or rom one molecular proportion of cyanuric chloride and two molecular proportions of 1-(3-a1nino) -phenyl-5-pyrazolone-3-carboxylic acid (a brownish powder, insoluble in acids, easily soluble in alkalies The new product corresponds very pro ably with the formula COOH Example 8.

If in the herein described process such a compound is chosen as component of the sec- 100 0nd phase, which contains at two difierent itions of its molecule mobile atoms of drogen, such as for instance, a diamine, t are is thus formed a condensation product of the second phase which contains two cylnl anuric residues.

a. J-N\N N-ii d4; 5 -g Or. a a JH.

coon

until the components have disappeared, neu traliied with soda, and the solutionpi the t primary condensation product thus gbt ained is treated with 10.8 parts of" phenylenediamine and stirred during several houi's at The product is precipitated out of its solution-by means of acid and is characterized by the presence of two amino-groups and two mobile atoms of chlorine.

E :mmple 4.

An iced aqueous suspension of 18.5 parts of cyanuric chloride is treated with an aqueous solution of 21 parts of 1:3-phenylenediaminel-sulfonate of sodium. The acid disappears rapidly under formation of the corresponding primary condensation product. bonate, a solution of 26.1 parts of 2: 5-aminonaphthol-i-sulfonate of sodium in 200 parts of water is added, while stirring,-at about- 20 0., until the aminonaphtholsulfonic acid has almost completely disappeared. The isolated product contains a free diazotizablc amino-group.

Ewample 5.

31.9 parts of 1:8-aminonaphthol-3:6-disulfonic acid are dissolved by means of 13.3 parts of caustic soda solution of 30 per cent strength, treated with 18.5 parts ofcyanuric.

common salt and acid and forms a light colored precipitate which is more easily soluble than the starting material; In; alkaline solutions do not fluoresce, and it is characterized by the presence'of' one mobile atom of chlorine. c

By treatment of the primary condensation product with ammonia, diethylamine or acetam'ide in the cold orat ordinary tem perature, there is formed' in an analogous mannerthe secondary condensation product from one molecular roportion' of cyanuric chloride, one molecu ar-proportion of 1:8- aminonaphthol-3 :6-disulfonic acid and one molecular proportion of ammonia or diethylamine or acetamide. .All thesegpro'ducts are After neutralizing with sodium carmobile atom of chlorine."

The (ii-secondary product thus obtained has the formula:

NIH 3 also characterized by their great solubility, by their alkaline solutions which do not fluoresce, and by the presence of one mobile atom of chlorine. sponds very probably with the general formula: Y

Cl C-R HOaS- 80 K in which --R means OH, or NH,, or

cocm Example 6.

If a freshly prepared solution of the condensation. product from one molecular proportion of cyanuric' chloride and one molecular roportion of 1:8-aminonaphthol- 3:6-disu fonic acid is treated first with 30 parts of crystallized sodium acetate and then with a solution of 12.9 parts of aniline hydrochloride, the aniline disappears completely while stirring and a secondary con ensation product from one, molecular proportion of cyanuric chloride, one molecular proportion of 1:8-aminonaphthol-3z6- disulfonic acid, andone molecular proportion of aniline is formed. This new secondary condensation product is precipitated by means of common salt and forms, when :dry, a grey powder easily soluble in alkalies without fluorescence.

With other primary or secondary amines instead of aniline there are obtained the corresponding secondary condensation products. Among such'products there'may be named those obtained by means of the fol.-'

lowing amino-derivatives: p-aminoacetani- -lide, m-aminoformanilide, In-aminobenzoic acid, 0- and -p'-aminosalicylic' acid, -chloro- 6-aminos'alicylic acid, -sulfo-fi-aminosalicylic, acid, aniinophthalic acid, and the like. All these secondary condensation products form grey powders; their alkaline solutions dovnot .fluoresce, andthey The new product correcontain still one E'wample '7'.

18.5 parts of cyanuric chloride are suspended in about 1000 parts of water and treated by and by, While stirring-at 0 C. with 26.2 parts of 2:5-aminonaphthol-7-sulionic acid, keeping the mixture always slightly acid by addition of a solution of sodium carbonate. As soon as the whole is dissolved and no more aminonaphthol can be traced, the liquid is treated with a solution of 17.4 parts of m-nitraniline in 300 parts of water and gently warmed. The secondary condensation product from one molecular proportion of cyanuric chloride, one molecular proportion of 2:5-aminonaphthol-T-sultonic acid, and one molecular proportion of m-nitranilineforms a yellow ish powder, which is soluble in allralies with slightly yellow coloratiolr without fluorescence.

In'an analogous manner there are obtainedother secondary condensation products r'rom'l molecular proportion of eye k f tion product, when' dried, forms a grey miricchloride, one molecular proportion 0 2:5-aminonaphthol-7-sulfonic acid, and one molecular proportion of m-nitraniline. or one molecular proportion of another aromatic compound, such as for instance, aniline and its liomologues, pand iii-phenylcnediamine, maminoformanilide. All these products form grey powders which dissolve in alkalies without fluorescence, and those containing free ammo-groups are capable of yielding diam-compounds with nitrite and mineral acids.

Example 8.

sodium phenolate and stirred until the liquid becomes, neutral. The secondary con- .densation product from one molecular proportion of cyanurlc chlor de, one molecular proportion of 2 :S-aminonaphthol-6sulfonic 'acid,. and one"molecular proportion of phenol thus obtained is precipitated with ydrochloric acid. It forms a grey powder. soluble without fluorescence in alkalies and 4 characterized by the presence of one mobile atom of chlorine andcorresponds very probably with the formula:

-on I n mh ilz g Ewample 9.

31.?) parts of 1:8-aminonaphthol-3:6-disulfonic acid are dissolved b means of 13.3 parts of caustic soda so ution of 30% strength, treated with 18.5 parts .ofcya nuric chloride and stirred until all the components have disappeared. The solution thus obtained of the primary condensation product is neutralized very carefully and almost exactly, and treated with a solution of 31 parts of 1:8-aminonaphthol-3:6-disulionic acid, 13.3 parts of caustic soda solution oi 30 per cent strength, 30 parts of sodium acetate and 150 parts 10f water. After stirring for half an hour to one hour, the 1:8-an'1inonaphthol-3 :(S-disulfonic acid has disappeared and the secondary condensation product from one molecular proportion or cyanuric chloride and two molecular proportions of1:8-aminonaphth0l-3 :6- '(llSlllfOIllQ acid has precipitated partly.

The precipitatiomis completed by the addition of common salt. The new condensae powder dissolving in alkalies without fluorescence. It contains. still one mobile atom of chlorine.

The corresponding secondary condensation product from one molecular proportion of cyanuric chloride and two. molecular proportions of 2: 5-aminonaphthol-7 -sulfonic acid may be obtained in the following manner:

i The solution of the primary condensation product from 18.5 parts of cyanuric chloride and 26.2 parts of the sodium salt of 2:5 aminonaphthol7sulfonic acid is neutralized in the cold with carbonate of sodium and there is added a freshsolution of 26.2 parts of sodium 2:5-au1inonaphthol-7-sulionate. This mixture is stirred until the aminonaphthol has almost completely disappeared.

By adding mineral acid and common salt there may be isolated from .the solution thus obtained the secondary condensatidn product from two molecular proportions of 2:5- aminonaphthol-7-sulfonic acid and one molecular proportion of cyanuric chloride in the form of a gre powder.

The new prot uct shows the following particularities: When its aqueous solution which does not fluoresce, is heated in the presence of sodium carbonate, it loses a part of its coupling capacity. Apart from this special reaction it behaves like the other secondary condensation products. Symmetrical secondary condensation products may be obtained in the same manner with other aminonaphthols, such as for instance, the 1:8-aminonaphthol-i-sulfonic acid andthe 2:8-aminonaphthol-G-sulfonic acid.-

Equally. easily, mixed derivatives ma be prepared by using in the two phases 0 the preparation of the secondary condensation 'product two dilierent aminonaphthols; for

instance the secondary condensationproduct from one molecular proportion of cyanuric chloride, one molecular proportion of 1:8- aminonaphthol-3:G-disulfonic acid, and one molecular proportion of 2: 5-aminona-phthol- 7-sulfonic acid can be obtained by treating the solutions of the. primary condensation iv product from one molecular proportion of V cyanuric chloride and one molecular proportion of 1 8-a1ninonaphthol-3: (i-disulfonate of sodium with the aqueous solution of one molecular proportion of 2 5-aminonaphthol- 7-sulfonate of sodium or,-0n the contrary, by treating the primary condensation product from one molecular proportion of cyanuric chloride' and one molecular proportion of 2:5-a1ninonaphthoL'f-sulfonic acid with one molecular proportion of 1 8-aminonaphthol-3:6 disulfonate of sodium. The two processes yield the same condensation product which forms a grey powder.

'It corresponds Very probably with the "formula: W

Example 10.

no ZEN-O0 7 Example 11. The solution of the primary condensation product from one molecular proportion of cyanuric-chloride and one molecular proportion .of 2:5-aminonaphthol-7-sulfonic acid 7 .is treated with an aqueous 'solution of 5.04 parts (one half molecula proportion) of owder yield To a solution of the primary condensa- Orin iOfifi sou! I 3 v w i I YL QET ich does not until nearly all the last named sulfonic acid has disappeared. The solution then contain" the secondary condensation product which may be isolated byadding common salt. It is a grey powder which is soluble in alkalies 1:01 a solution which does not fluoresce, and

,which contains a mobile atom ofphlorine.

Itis also possible to combine together by means of cyanuric chloride aminonaphthols which are more complicated.

108.6 partsof the reduced N-condensation product from nitrobenzoylchloride and 1- 3-aminobenzoyl) -amino8-naphthol-;3 6- disulfonic acid are dissolved in water by v means of 26.6 parts of caustic soda solution of 30 per cent strength, and then treated, first in the cold, and afterwards by slight heating, with 18.5 arts of cyanuric chlorlde in a fine state of Sn division. The secondary condensation product thus obtained isprecipitated b means of hydrochloric acid, filtered and ried. It is a grey powder, soluble in alkalies to a solution which is not fluorescent. The new product corresponds'very probably with the formula p-phenylen ediamine. By neutralizing the formed hydrochloric acid and gently warming, the condensation is achieved. From this solution there can be separated, by adding common salt, the substances having properties corresponding with the formula:

' What we claim 1. The herein described process of pro duo: ing new intermediate products for the synthesis of azo-dyes, which consists in condensmg, in a first phase, one molecular proportion of a cyanuric trihalide with one wherein R,, and R, represent the same or itferent alkyl, aryl or aralkyl radicals or a hydrogen atom), and thirdly, containing at least one strong acid group, then condensing, in a second phase, at least one molecular proportion of the products thus obtained with one molecular proportion of one of a group of compounds which contains at least one amino or one hydroxyl group, at least one of the two phases being carried out in water. a v 2. The herein described process of producing new intermediate products for the synthesis of azo-dyes, which consists in condensing, in a first phase, one molecular proportion of a cyanuric trihalide with one molecular proportion of a compound of the aromatic series derived from a hydrocarbon which contains not more than 10 carbon atoms and having, firstlypa non-tertiary amino group, secondly, still containing at least one of a group of auxochromes includmg R. a -0H CH co- N- N- 'R, MD

(wherein R and R, represent the same or different alkyl, aryl or aralkyl radicals or a'hydrogen atom), and thirdly, containing at least one strong acid group, then condensing, in a second phase, at least one molecular proportion of the products thus obtained with one molecular pro ortion of one of a group of compounds Wl'llCll contains at least one amino or one hydroxyl group, at least one of the two phases being carried out in water.

3. The herein described process of producing new intermediate products for the synthesis of azo-dyes, which consists in condensing, in a first phase, one molecular proportion of cyanuric trihalide with one molec ular proportion of a primary aromatic amine derived from a hydrocarbon which contains not more than 10 carbon atoms and having still at least'one of a group of auxochromesincluding R. moo/ (wherein It, and R, represent the same or different alkyl, aryl or aralkyl radicals or a hydrogen atom), and which contains at least one strong acid-group, then condensing, in a second base, at least one molecular proportion 0 the products thus obtained with chromes including contains not more than 10 carbon atoms and having still at least one of a group of auxo- (wherein R, and R represent the same, or different alkyl, aryl or aralkyl radicals or a hydrogen atom), and which contains at least one sulfo group, then condensing, in a second "phase, at least one molecular proportion of the products thus obtained with one molecular proportion of one of a group of compounds which contains at least one amino or one hydroxyl group, at least one of the two phases being carried out in water.

5. The herein described process of producing new intermediate roducts for the synthesis ofazo-dyes, whie 1 consists in condensing, in a first phase, one molecular proportion of a cyanuric trihalide with one molecular proportion of a primar aromatic amine derived from a hydrocar on which contains not more than 10 carbon. atoms and having still at least one of a group of auxochromes including (wherein It and R represent the same or different alkyl, aryl or aralkylradicals or 'a'hydrogen atom), and which contains at least one sulfo group, then condensing, in a. second phase, at least one molecular proportion 0' the products thus obtained with one molecular proportion of an aromatic amino compound which carries hydrogen atoms capable of being exchanged in amino groups, atleast one of the two phases being carried out in water.

:6. The herein described" process of producing new intermediate roducts for the synthesis of azo-dyes, whic consists in con- (lensing, in a first phase, one molecular proportion of a cyanuric trihalide with one molecular proportion of a primar aromatic amine derived from a hydrocar on which contains not more than 10 carbon atoms and having still at least one of a group of auxochromes including (wherein B and R3, repiesentthe same or dilferentalkyl, aryl or aralkyl radicals or a hydrogen atom), and which contains at least one sulfo group, then condensing, in a second phase, one molecular proportion of the products thus obtained with one molecular proportion of an aromatic amino compound which COIltillllS at least, one pr mary ammo group, at least one of the two phases beingv carried out in .water. j

7. The herein described new lntermediate products for the synthesis of azo'-dyes.of the general formula:

Halogen I \N ,a

N all wherein R means an aromatic residue which,

firstly, containsat least one strong acid group, secondly, contains'at least one of a group of auxochromes including (wherein R, and R represent the same or different alkyl, aryl or aralkyl radicals or a hydrogen atom), Q, a hydrogen atom or a radical which are linked to the carbon atom of the cyanuric nucleus by,one of a group of connecting links which contains 0 i or N,- and a a whole number not higher than the number of the mobile hydrogen atoms originally present in the amino and hydroxy groups of the compounds corresponding with the radical Q, which products form colorless to gray and yellowish powders 'WlllCll dissolve in solvents formlng from colorless'to yellow and brownish to yellow and brownish solutions, and which are char-' acterized by the presence of a mobile atom of halogen at the cyanuric nucleus.

8. The herein described new intermediate 7 products for the synthesis of azo-dy-es of the general formula:

I Halogen ssh t QQ N n wherein R means an aromatic residue de- 'rived from a hydrocarbon which contains not more than 10 carbon atoms and which,

firstly, contains at least one strong acid group, secondly, contains at least one ofa group of auxochromes including wherein R (and R5 represent the same or different alkyl, aryl or aralkyl radicals or a hydrogen atom), Q a hydrogen atom or a radical which are linked to the carbon atom of the cyanuric nucleus by one of a group of connecting links which contains 0 or N, and n, a whole number not higher than the number of the mobile-hydrogen atoms originally present in the amino and hydroxy groups of the compounds corresponding with the radical Q, which products are from colorless to gray andv yellowish powders [which dissolve in solvents forming from,

colorless to yellow and brownish'selutions,

and which are characterized by the presence of a mobile atom of halogen at the cyanuric nucleus. I

9. The herein described new intermediate products for the synthesis of azo dyes of the general formula:

,Halogcn wherein R means an aromatic residue which,

- firstly, contains at least one sulfo group,

secondly, contains at least one-of a group of auxoehromes including RbCO i Ru 7 -oH,-cH2oo--, (wherein R, and R represent the. same or different alkyl, aryl.-or aralkyl radicals or a hydrogen atom), R being an aromatic residue, and n a whole number not higherthan the number of the mobile hydrogen atoms originally present in the molecule of the radical R .10. 'Theherein described new intermediateproducts for the synthesis of azo-dyes of the generalformula:

Halogen aromatic compound, and n a whole number a smaller than three, whichproducts are from colorless to gray and yellowish powders which "dissolve in solvents forming from colorless to yellow and brownish solutions, and which are characterizedjby thepresence of a mobile atom of haIogen-at-the cyanuric i v is nucleus.

11 The herein described new intermediate wherein R, means an aromatic residue clerived from, a hydrocarbon which contalns i not more than 10 carbon atoms and which,

firstly, contains at least one sulfo group, secondly, COIltR'lIlS at least one of a group of auxochromes including '(wherein R and R represent the same or difierent alkyl, aryl or aralkyl radicals or a hydrogen atom), R being an aromatic residue, which products are from colorless to gray and yellowish powders which dissolve 1n solvents forming from colorless to yellow and brownish solutions, and which are characterized by the presence of a mobile atom of halogen at the cyanuric, nucleus.

- 12. The herein described new intermediate products for "the syiithesis vof azo-dyes of the general formula:

Halogen N/ \N R1-1;Iii d7-NR: H wherein R means an aromatic residue derived from zr hydrocarbon which contains not more than 10 carbon atoms and which, hrstly, contains at least one sul'fo group, secondly, contams at least one of a group of auxochromes including OHand NH R be-' ing a radical of an aromatic amino compound, which products are from colorless to gray and yellowish powders which dissolve in solvents forming from colorless to yellow and brownish solutions, and which are characterized by the presence of a mobile atomof halogen at the cyanurio nucleus.

In witness whereof we have hereunto signed our names this 6th day of July, 1923. HERMANN FRITZSCHE. EDUARD KRUMMENACHER. HANS GUBLER. OTTO KAISER. v 

